Synthesis and characterization of novel diazenes bearing pyrrole, thiophene and thiazole heterocycles as efficient photochromic and nonlinear optical (NLO) materials

Two series of novel thermally stable second-order nonlinear optical (NLO) and photochromic chromophores have been designed and synthesized. The two series of compounds were based on different combinations of donor groups (pyrrole or thienylpyrrole) which act simultaneously as π-conjugated bridges, together with diazoaryl or diazothiazolyl as acceptor moieties. Their photochromic and electrochemical behavior were characterized, while hyper-Rayleigh scattering (HRS) was employed to evaluate their second-order nonlinear optical properties. The results of these studies have been critically analyzed together with two other related compounds reported earlier from our laboratories in which the thienylpyrrole system was used as the donor group keeping the functionalized diazoaryl as acceptor moiety. The measured molecular first hyperpolarizabilities and the observed photochromic behavior showed strong variations for the different donor systems used (pyrrole or thienylpyrrole) and were also sensitive to the acceptor strength of the diazenehetero(aryl) moiety.The thienylpyrrole based compounds endowed with extended π-conjugated bridges and stronger donor auxiliary effects in comparison to the pyrrole compounds, when coupled to the stronger acceptor diazo(hetero)aryl groups gave rise to significantly larger hyperpolarizabilities (β = 274–415 × 10−30 esu) for an incident wavelength of 1064 nm. These compounds also displayed improved photochromic behavior with very fast response to the visible light stimulus (1.5 s) and fast thermal return to the original forms (2–3 s).

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► 1-Synthesis of novel azo dyes bearing thiophene, pyrrole and thiazole heterocycles.
► Use of pyrroles and thienylpyrroles as auxiliary donors in heterocyclic NLO materials.
► Characterization of thermal and electrochemical properties of heterocyclic azo dyes.
► Characterization of NLO and photochromic properties of donor–acceptor pyrrole azo dyes.
► This multidisciplinary study shows that these novel heterocyclic azo dyes are interesting candidates as solvatochromic probes, second-order NLO and photochromic materials.